CN107268014A - A kind of preparation method and application of titanium dioxide/carbon aerogels photocathode - Google Patents
A kind of preparation method and application of titanium dioxide/carbon aerogels photocathode Download PDFInfo
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- CN107268014A CN107268014A CN201710412812.0A CN201710412812A CN107268014A CN 107268014 A CN107268014 A CN 107268014A CN 201710412812 A CN201710412812 A CN 201710412812A CN 107268014 A CN107268014 A CN 107268014A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/55—Photoelectrolysis
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a kind of preparation method and application of titanium dioxide/carbon aerogels photocathode, this method is using butyl titanate as titanium source, by adding crystal face end-capping reagent, oxidant, prepare under hydrothermal conditions while having the Detitanium-ore-type TiO of { 101 } and { 001 } crystal face2It is nanocrystalline, then by the method for electrophoretic deposition by { 101 } { 001 } TiO2Nano particle is loaded on carbon silica aerogel electrode, prepares { 101 } { 001 } titanium dioxide/carbon aerogels photocathode material, is applied in production hydrogen field.Compared with prior art, the present invention has efficient photoelectrocatalysis reducing property, is applied to photoelectrocatalysis production hydrogen, 6h hydrogen outputs are up to 8.652Lmg under ultraviolet light‑1, and easily realize recycling, non-secondary pollution.
Description
Technical field
The present invention relates to clean energy resource and technical field of material chemistry, have { 101 }-{ 001 } crystal face different more particularly, to one kind
The nanoscale TiO of matter knot2The preparation method of/carbon aerogels photocathode, and the application in terms of efficient catalytic also originates in hydrogen.
Background technology
Hydrogen is a kind of clean energy resource, and photodissociation aquatic products hydrogen is a kind of environment-friendly and sustainable energy development approach.From
Ultraviolet excitation TiO was reported first from Honda and Fujishima in 19722Photoelectrocatalysis decomposes aquatic products hydrogen, and different is photoelectrochemical
Battery (PEC) system is designed to construct more efficient photoelectrocatalysimaterial material.Influence photoelectrocatalysis water decomposition it is crucial because
Element is that the hard to bear sunshine of semiconductor energy excites generation carrier, it is possible to efficiently separates, move to semiconductor and solution
Water reduction or oxidation reaction occur for interface.
At present, with the quick consumption of fossil fuel (coal, natural gas, oil), a kind of long-term sustainable is developed a large amount of
The regenerative resource of supply is extremely urgent.Solar energy fuel refers to that the system of chemical energy, such as H can be converted solar energy into2、
Methanol, methane etc., it is considered to be solve future source of energy and the most potential strategy of environmental problem.H2It is development low-carbon economy
Compared with a kind of energy carrier of most potential and advantage, the energy that gasoline, coal combustion with phase homogenous quantities are provided, the production of hydrogen
Heat highest and burning final product there was only water generation, to surrounding environment without any harm, be accordingly regarded as " green energy resource ".
The core of photoelectrocatalysis hydrogen production by water decomposition reaction is the photoelectrocatalysis agent material for developing excellent performance.It is used as one
Plant n shape conductor photocatalysis materials studied earliest, TiO2Be widely used in the depollution of environment, self-cleaning material, production hydrogen,
The fields such as light compositing, organic synthesis and solar cell.In numerous semiconductor photoelectrocatalysielectrode materials, TiO2With it is inexpensive,
Nontoxic, stability is good, advantages of environment protection, thus has obtained extensive research, and is considered as light most with prospects
Electrocatalyst materials.However, TiO2Broad stopband (3.2eV) make it can only be by wavelength<385nm ultraviolet excitation is utilized (only
Account for solar spectrum energy 5%), secondly TiO2The light induced electron of presence and the disadvantage such as hole is higher to recombination rate, urge its light
Change activity relatively low.In view of problem above, for TiO2Modification carried out by numerous scientific workers it is extensive and deep
Research.
In order to improve the photocatalysis performance of titanium dioxide, researcher is constantly attempting recently, it is desirable to specific by preparing
Active crystal face, so as to improve the photocatalysis performance of material.But, if certain single crystal face proportion is too high, occur excessive
Go out effect, because light induced electron and accumulation of the hole on single crystal face, can improve its recombination probability so that electronics and sky
Cave can not be effectively separated, and be transferred to interface and reacted.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of titanium dioxide/carbon gas
The preparation method of gel photocathode.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of a kind of titanium dioxide/carbon aerogels photocathode, using butyl titanate as titanium source, by adding crystal face
End-capping reagent, oxidant, are prepared while having the Detitanium-ore-type TiO of { 101 } and { 001 } crystal face under hydrothermal conditions2Nanometer
Crystalline substance, then by the method for electrophoretic deposition by { 101 }-{ 001 } TiO2Nano particle is loaded on carbon silica aerogel electrode, is prepared
{ 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material, specifically includes following steps：
(1) butyl titanate is weighed, then end-capping reagent and oxidant are added dropwise successively, 10~30min is stirred, obtains presoma molten
Liquid, is then moved in reactor, 18~24h of hydro-thermal reaction in 180~220 DEG C of temperature ranges is put into baking oven after sealing, instead
After should terminating, reactor is cooled to room temperature, product is centrifuged, and is cleaned multiple times with deionized water, ethanol, is cleaned
After complete, sample is placed in vacuum drying chamber, 12~24h is dried at 60~80 DEG C；
(2) { 101 } for preparing step (1)-{ 001 } TiO2Nano particle ultrasonic disperse is in acetone, Ran Houjia
Enter elemental iodine, using carbon aerogels as negative electrode, titanium plate causes the distance between two electrodes to keep 2cm as anode, 10~
0.5~1h is deposited under 15V voltages, above-mentioned material is deposited on carbon aerogels, electrode is taken out and is placed in vacuum by deposition after finishing
12~24h is dried in drying box at 60~80 DEG C, that is, prepares { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode
Material.
End-capping reagent described in step (1) is hydrofluoric acid, and described oxidant is hydrogen peroxide, described in step (1)
Butyl titanate, end-capping reagent, the volume ratio of oxidant are 5：(0~0.6)：(0~6).
{ 101 }-{ 001 } TiO in step (2)2The addition of nano particle in acetone is 40~50mg/50~100mL
Acetone, { 101 }-{ 001 } TiO2The mass ratio of nano particle and elemental iodine is 40~50：10~20.
Application of the titanium dioxide the prepared/carbon aerogels photocathode in production hydrogen, in sealing gas circulating system
Three electrode reactors of self-control and vacuum air-channel are equipped with, work is used as using { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material
Making electrode, (wherein { 101 } ratio is 15~85%, and { 101 } crystal face exposure ratio is the addition by end-capping reagent and oxidant
To regulate and control), titanium plate is as to electrode, and saturated calomel electrode (SCE) is containing 0.3~0.8mol L as reference electrode-1KOH
In the aqueous solution of electrolyte, apply -0.6~-0.3V (vs.SCE) biass under ultraviolet light, divide so as to be realized in photocathode
Xie Shui produces hydrogen, and hydrogen output is 0.172~1.442Lh-1·mg-1。
The electronic structure of { 001 } that is obtained by DFT theoretical calculations and { 101 } two crystal faces shows, { 101 } crystal face and
{ 001 } crystal face has equal fermi level due to contacting with each other, secondly { 101 } crystal face and { 001 } crystal face upper surface electronics
The difference that structure is present so that { 101 } valence band current potential ratio { 001 } crystal face corrigendum of crystal face, both valence band minimum difference positions
In the both sides of fermi level.Meanwhile, conduction band positions ratio { 101 } crystal face of { 001 } crystal face it is more negative so that in { 101 } and { 001 }
The crystal face heterojunction structure of material itself can be formed between two crystal faces.This structure is more beneficial for photo-generate electron-hole pair
Separation and transfer, i.e., light induced electron to { 101 } crystal face migrate, photohole to { 001 } crystal face migrate, so as to effectively facilitate
Electronics and hole are efficiently separated.On this basis, the ratio that { 101 } crystal face and { 001 } crystal face expose is to TiO2Photocatalytic
There can be obvious influence.
On the other hand, in order to solve crystal face hetero-junctions TiO2Loading problem of the material on electrode, and it is inclined by applying
Pressure improves the separative efficiency in light induced electron and hole.Choose it is a kind of with high conductivity, high capacity rate base material also very
It is necessary.Carbon aerogels (CA) are as a kind of amorphous carbon block materials with continuous three-dimensional net structure, and specific surface area is big,
Porosity is high, and with high conductivity, high thermal stability, simple and easy to get and low cost and other advantages are widely used as catalyst
Carrier.
Therefore the present invention chooses carbon silica aerogel electrode as substrate, using the method for electro-deposition, constructs nanoscale crystal face different
Matter knot { 101 }-{ 001 } TiO2/ CA photocathodes, not only remain the TiO with crystal face hetero-junctions2The premium properties of nano particle,
And further strengthen the photoelectric catalytically active of electrode by the excellent chemical property of carbon aerogels, it is adaptable to efficiency light
Electro-catalysis production hydrogen field.
Compared with prior art, the present invention has advantages below：
(1) with commercialization TiO2The photocathode material that nano particle (P25) is constructed is compared, and { 101 } prepared by the present invention-
{001}TiO2Due to being prepared for that there is excellent photocatalysis property with specific high activity crystal face.
(2) it is dominant ({ 101 } crystal face ratio be 85%) with { 101 } crystal face and { 001 } crystal face is dominant ({ 101 } crystal face ratio
For nano-TiO 15%)2/ CA is compared, and { 101 } crystal face ratio is 49% nanometer { 101 }-{ 001 } TiO2/ CA electrodes, in purple
Hydrogen output highest under outer light irradiation, is the above two 1.42 times and 8.38 times respectively.This is due to { 101 } and { 001 } crystal face
After ratio optimization, the presence of crystal face hetero-junctions can promote light induced electron and hole can be effectively directed migrate respectively to
{ 101 } crystal face and { 001 } crystal face.So as to effectively increase TiO2Nano particle light excites the separation in rear electronics and hole to imitate
Rate, while the spills-over effects for avoiding excessive accumulation of the electronics on { 101 } crystal face and causing, and electronics and hole are answered
Close.
(3) { 101 }-{ 001 } TiO prepared by the invention2Size is nanoscale, thus nano effect, the surface area of material
Effect and carrier diffusion effect will be embodied well, so that the activity of its light-catalyzed reaction is further changed
It is kind.
(4) the carbon aerogels matrix that the invention is used, its multi-pore channel structure is conducive to { 101 }-{ 001 } TiO2Attachment,
And its high-specific surface area can be crystal face hetero-junctions TiO2Load more avtive spots are provided, in addition, carbon aerogels have in itself
There is very excellent electric conductivity, by being biased, can accelerate to promote TiO2The transfer of light induced electron, promotes itself and photoproduction
The separation in hole, realizes efficient photoelectric-synergetic effect.
Brief description of the drawings
Fig. 1 is { 101 }-{ 001 } TiO prepared by embodiment 12The scanning electron microscope (SEM) photograph of/CA electrodes；
Fig. 2 is { 101 }-{ 001 } TiO of different crystal faces exposure ratios in embodiment 1,2 and 42/ CA electrode photodissociation aquatic products hydrogen
With the relation curve of time.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following examples will be helpful to this area
Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the general of this area
For logical technical staff, without departing from the inventive concept of the premise, various modifications and improvements can be made.These are belonged to
Protection scope of the present invention.
Embodiment 1
{ 101 } crystal face exposure is than the nano-TiO for 49%2The preparation method of particle, the feature of this method includes following step
Suddenly：
By adjusting the addition of end-capping reagent, oxidant, weigh butyl titanate, then be added dropwise successively end-capping reagent hydrofluoric acid and
Oxidants hydrogen peroxide, butyl titanate, end-capping reagent, the volume ratio of oxidant are 5：0.2：6, so as to prepare { 101 } crystal face
Exposure is than the TiO for 68%2Nano particle, solution uses magnetic stirrer during being added dropwise, and 30ml is moved to after being added dropwise to complete
In the stainless steel cauldron of polytetrafluoroethyllining lining, then it is placed in reaction 24h in 200 DEG C of baking ovens.It is after reaction terminates, reactor is cold
But to room temperature, product is centrifuged, and is cleaned multiple times with deionized water, ethanol.After having cleaned, sample is placed in vacuum
In drying box, 12h is dried at 80 DEG C.
The morphology characterization of electrode is shown in Fig. 1, as a result shows TiO2Tetragonal bipyramid shape particle, TiO are blocked for size about 50nm2
Network duct growth of the particle along carbon aerogels surface.
Embodiment 2
{ 101 } crystal face exposure is than { 101 }-{ 001 } TiO for 49%2The preparation of/CA electrodes, the feature of this method includes
Following steps：
(1) by adjusting the addition of end-capping reagent, oxidant, butyl titanate is weighed, then end-capping reagent hydrogen fluorine is added dropwise successively
Acid and oxidants hydrogen peroxide, butyl titanate, end-capping reagent, the volume ratio of oxidant are 5：0.2：6, so as to prepare { 101 }
Crystal face exposure is than the TiO for 49%2Nano particle, solution uses magnetic stirrer during being added dropwise, and is moved to after being added dropwise to complete
In the stainless steel cauldron of 30ml polytetrafluoroethyllining linings, reaction 24h in 200 DEG C of baking ovens is placed in.After reaction terminates, by reactor
Room temperature is cooled to, product is centrifuged, and is cleaned multiple times with deionized water, ethanol.After having cleaned, sample is placed in very
In empty drying box, 12h is dried at 80 DEG C.
(2) electrophoretic deposition technique is used, using carbon aerogels as negative electrode, using titanium plate as anode, ultrasonic disperse 40mg steps
(1) { 101 } ratio obtained in is 49% { 101 }-{ 001 } TiO2Nano particle, 10mg elemental iodines in 50mL acetone,
30min is deposited under 10V voltages.After deposition terminates, electrode is taken out, and 12h is dried in vacuo at 80 DEG C, that is, is obtained final
{101}-{001}TiO2/ CA electrodes.
Embodiment 3
Using three-electrode system, under the conditions of 25 DEG C, photoelectrochemical behaviour is carried out on CHI 660c electrochemical workstations
Test, respectively using saturated calomel electrode (SCE) and Pt as reference electrode and to electrode, and with 0.5mol L-1KOH is electrolysis
Matter solution, to { 101 }-{ 001 } TiO that { 101 } ratio is 49%2/ CA optoelectronic poles carry out LSV curves and ampere i-t curves are surveyed
Examination.Compared to { 101 } TiO of the high single crystal face of exposure2/ CA and { 001 } TiO2/ CA, { 101 } that { 101 } ratio is 49%-
{001}TiO2/ CA has maximum hydrogen-evolution overpotential, is -1.1V (vs SCE), while having highest photocurrent response value (Δ I
=-6.773 × 10-6A)。
Embodiment 4
Using { 101 }-{ 001 } TiO2/ CA electrode photoelectrics decompose the experiment of aquatic products hydrogen, and this method specific steps include as follows：
KOH solution from 0.5mol/L carries out producing hydrogen test for electrolyte solution in 25 DEG C of stirrings of constant temperature.With
{101}-{001}TiO2/ CA electrodes are working electrode, and using Ti plates as to electrode, saturated calomel electrode (SCE) is reference electrode,
Irradiated, biased by application -0.4V with all-wave light source, (be equipped with thermal conductivity to pass in the AG photocatalysis on-line analysis systems of LabSolar- III
Sensor (TCD)) on carry out production hydrogen test with analysis.By the AG photocatalysis on-line analysis systems of LabSolar- III and gas chromatograph
(GC) it is combined, every 1 hour direct injected into gas chromatograph, and carries out qualitative analysis and quantitatively detect H2Yield, often
Individual 6 hours of sample detection.
Test result shows, { 101 }-{ 001 } TiO2/ CA electrodes are successfully realized the photoelectrocatalysis reduction point of efficient stable
Aquatic products hydrogen is solved, Fig. 2 is seen.Increase over time, the growth of the hydrogen output of sample over time constantly increases, and with good
Linear relationship, shows that the production stabilized hydrogen of electrode material is good.{ 101 }-{ 001 } TiO in this embodiment2Nanocrystalline
{ 101 } crystal face ratio is 49%, and its hydrogen output is up to 1.442Lh-1·mg-1.Decomposed in photoelectrocatalysis under aquatic products hydrogen, nanometer
Level crystal face hetero-junctions { 101 }-{ 001 } TiO2The hydrogen production potential of/CA electrodes is not only above business TiO2Nano particle (P25) is constructed
Optoelectronic pole material, be also significantly better than the TiO of high single { 101 } crystal face of exposure and { 001 } crystal face2/ CA electrodes are (respectively
0.172L·h-1·mg-1And 1.017Lh-1·mg-1), see Fig. 2.
In addition, also disclosing the exposure of { 101 } crystal face in Fig. 2 than for 15%, 85% and common P25/CA electrode photodissociation
Aquatic products hydrogen and the relation curve of time, it can be seen that it is 49% that hydrogen output highest electrode, which is { 101 } crystal face ratio,
{101}-{001}TiO2/ CA electrodes.Because, { 001 } crystal face of height exposure due on surface main accumulation be that photoproduction is empty
Cave, therefore reproducibility is poor, so the effect of production hydrogen is worst；On the other hand, on { 101 } crystal face main accumulation be photoproduction electricity
Son, therefore with stronger reducing property.But be not { 101 } crystal face exposure than higher, the ability of also original hydrogen is stronger,
Because { 101 } crystal face coexists with { 001 } crystal face in crystal growth, when the continuous improvement of the exposure ratio of { 101 } crystal face,
{ 001 } the ratio regular meeting of crystal face reduces therewith, and the photohole now accumulated on the crystal face can reach hypersaturated state and produce
Spills-over effects, neutralize the light induced electron on { 101 } crystal face, reduce the reducing property of { 101 } crystal face.When the ratio of two kinds of crystal faces is excellent
After change, there is synergy in interplanar, crystal face hetero-junctions enhances light induced electron and the directional migration ability in hole and separation is imitated
Rate, improves { 101 }-{ 001 } TiO2/ CA also originates in the ability of hydrogen.
Embodiment 5
The preparation method of a kind of titanium dioxide/carbon aerogels photocathode, using butyl titanate as titanium source, by adding crystal face
End-capping reagent, oxidant, are prepared while having the Detitanium-ore-type TiO of { 101 } and { 001 } crystal face under hydrothermal conditions2Nanometer
Crystalline substance, then by the method for electrophoretic deposition by { 101 }-{ 001 } TiO2Nano particle is loaded on carbon silica aerogel electrode, is prepared
{ 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material, specifically includes following steps：
(1) by adjusting the addition of end-capping reagent, oxidant, butyl titanate is weighed, then end-capping reagent hydrofluoric acid, titanium is added dropwise
Sour four butyl esters, end-capping reagent, the volume ratio of oxidant are 5：0.6：0, so as to prepare the exposure of { 101 } crystal face than the TiO for 15%2
Nano particle, stirs 10min, obtains precursor solution, then move in reactor, is put into after sealing in baking oven in 180 DEG C of water
Thermal response 24h, after reaction terminates, is cooled to room temperature by reactor, product is centrifuged, and with deionized water, ethanol
It is cleaned multiple times, after having cleaned, sample is placed in vacuum drying chamber, 24h is dried at 60 DEG C；
(2) { 101 } for preparing step (1)-{ 001 } TiO2Nano particle ultrasonic disperse in acetone, { 101 }-
{001}TiO2The addition of nano particle in acetone is 40mg/50mL acetone, then adds elemental iodine, { 101 }-{ 001 }
TiO2The mass ratio of nano particle and elemental iodine is 40：10.Using carbon aerogels as negative electrode, titanium plate causes two as anode
The distance between electrode keeps 2cm, deposits 1h under 15V voltages, above-mentioned material is deposited on carbon aerogels, after deposition is finished
Electrode is taken out to be placed in vacuum drying chamber at 60 DEG C and dries 24h, that is, prepares { 101 }-{ 001 } titanium dioxide/carbon gas
Gel photocathode material.
The application of titanium dioxide/carbon aerogels photocathode uses following methods：It is equipped with certainly in sealing gas circulating system
Three electrode reactors and vacuum air-channel are made, work electricity is used as using { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material
Pole, titanium plate is as to electrode, and saturated calomel electrode (SCE) is containing 0.3molL as reference electrode-1KOH electrolyte it is water-soluble
In liquid, application -0.6V (vs.SCE) is biased under ultraviolet light, so as to realize that decomposition water produces hydrogen in photocathode, produces hydrogen
Measure as 0.172Lh-1·mg-1。
Embodiment 6
The preparation method of a kind of titanium dioxide/carbon aerogels photocathode, using butyl titanate as titanium source, by adding crystal face
End-capping reagent, oxidant, are prepared while having the Detitanium-ore-type TiO of { 101 } and { 001 } crystal face under hydrothermal conditions2Nanometer
Crystalline substance, then by the method for electrophoretic deposition by { 101 }-{ 001 } TiO2Nano particle is loaded on carbon silica aerogel electrode, is prepared
{ 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material, specifically includes following steps：
(1) by adjusting the addition of end-capping reagent, oxidant, butyl titanate is weighed, then end-capping reagent hydrogen fluorine is added dropwise successively
Acid and oxidants hydrogen peroxide, butyl titanate, end-capping reagent, the volume ratio of oxidant are 5：0：0, so that it is brilliant to prepare { 101 }
Face exposure is than the TiO for 85%2Nano particle, magnetic agitation 30min obtains precursor solution, then moved in reactor, close
It is honored as a queen and is put into baking oven in 220 DEG C of hydro-thermal reaction 18h, after reaction terminates, reactor is cooled to room temperature, product is centrifuged
Separation, and be cleaned multiple times with deionized water, ethanol, after having cleaned, sample is placed in vacuum drying chamber, dried at 80 DEG C
12h；
(2) { 101 } for preparing step (1)-{ 001 } TiO2Nano particle ultrasonic disperse in acetone, { 101 }-
{001}TiO2The addition of nano particle in acetone is 50mg/100mL acetone, then adds elemental iodine, { 101 }-{ 001 }
TiO2The mass ratio of nano particle and elemental iodine is 50：20.Using carbon aerogels as negative electrode, titanium plate causes two as anode
The distance between electrode keeps 2cm, deposits 0.5h under 10V voltages, above-mentioned material is deposited on carbon aerogels, deposition is finished
Afterwards electrode is taken out to be placed in vacuum drying chamber at 80 DEG C and dry 12h, that is, prepare { 101 }-{ 001 } titanium dioxide/carbon
Aeroge photocathode material.
The application of titanium dioxide/carbon aerogels photocathode, it is characterised in that self-control is equipped with sealing gas circulating system
Three electrode reactors and vacuum air-channel, using { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material as working electrode,
Titanium plate is as to electrode, and saturated calomel electrode (SCE) is containing 0.8molL as reference electrode-1The aqueous solution of KOH electrolyte
In, application -0.3V (vs.SCE) is biased under ultraviolet light, so as to realize that decomposition water produces hydrogen, hydrogen output in photocathode
For 1.017Lh-1·mg-1。
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (8)
1. the preparation method of a kind of titanium dioxide/carbon aerogels photocathode, it is characterised in that this method is using butyl titanate as titanium
Source, by adding crystal face end-capping reagent, oxidant, is prepared while having the sharp of { 101 } and { 001 } crystal face under hydrothermal conditions
Titanium ore type TiO2It is nanocrystalline, then by the method for electrophoretic deposition by { 101 }-{ 001 } TiO2Nano particle loads to carbon aerogels electricity
On extremely, { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material is prepared.
2. the preparation method of a kind of titanium dioxide/carbon aerogels photocathode according to claim 1, it is characterised in that should
Method specifically includes following steps：
(1) butyl titanate is weighed, then end-capping reagent and oxidant are added dropwise successively, 10~30min is stirred, obtains precursor solution,
Then move in reactor, 18~24h of hydro-thermal reaction in 180~220 DEG C of temperature ranges, reaction knot are put into baking oven after sealing
Shu Hou, room temperature is cooled to by reactor, and product is centrifuged, and is cleaned multiple times with deionized water, ethanol, has been cleaned
Afterwards, sample is placed in vacuum drying chamber, 12~24h is dried at 60~80 DEG C；
(2) { 101 } for preparing step (1)-{ 001 } TiO2Then nano particle ultrasonic disperse adds iodine list in acetone
Matter, using carbon aerogels as negative electrode, titanium plate causes the distance between two electrodes to keep 2cm as anode, in 10~15V electricity
Pressure 0.5~1h of deposition, above-mentioned material is deposited on carbon aerogels, and electrode is taken out and is placed in vacuum drying chamber by deposition after finishing
In at 60~80 DEG C dry 12~24h, that is, prepare { 101 }-{ 001 } titanium dioxide/carbon aerogels photocathode material.
3. a kind of preparation method of titanium dioxide/carbon aerogels photocathode according to claim 2, it is characterised in that step
Suddenly the end-capping reagent described in (1) is hydrofluoric acid, and described oxidant is hydrogen peroxide.
4. a kind of preparation method of titanium dioxide/carbon aerogels photocathode according to claim 2, it is characterised in that step
Suddenly butyl titanate described in (1), end-capping reagent, the volume ratio of oxidant are 5：(0~0.6)：(0~6), is blocked by adjusting
Agent, the addition of oxidant, so as to prepare the TiO that different { 101 } crystal faces expose ratio2Nano particle.
5. a kind of preparation method of titanium dioxide/carbon aerogels photocathode according to claim 2, it is characterised in that step
Suddenly { 101 }-{ 001 } TiO in (2)2The addition of nano particle in acetone is 40~50mg/50~100mL acetone.
6. a kind of preparation method of titanium dioxide/carbon aerogels photocathode according to claim 2, it is characterised in that step
Suddenly { 101 }-{ 001 } TiO in (2)2The mass ratio of nano particle and elemental iodine is 40~50：10~20.
7. application of the titanium dioxide/carbon aerogels photocathode that such as claim 1 or 2 is prepared in production hydrogen.
8. the application of a kind of titanium dioxide/carbon aerogels photocathode according to claim 7, it is characterised in that in sealing
Three electrode reactors of self-control and vacuum air-channel are equipped with gas circulation system, with { 101 }-{ 001 } titanium dioxide/carbon aerogels light
Cathode material as working electrode, titanium plate as to electrode, saturated calomel electrode (SCE) as reference electrode, containing 0.3~
0.8mol L-1In the aqueous solution of KOH electrolyte, apply -0.6~-0.3V (vs.SCE) biass under ultraviolet light, so that
Photocathode realizes that decomposition water produces hydrogen, and hydrogen output is 0.172~1.442Lh-1·mg-1。
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